TWI288759B - Polyurethane/ureas useful for the production of spandex and a process for their production - Google Patents

Abstract

Segmented polyurethane/ureas useful in the production of spandex are produced by chain extending an isocyanate-terminated prepolymer in the presence of a solvent. The isocyanate-terminated prepolymer is formed by reacting a stoichiometric excess of an isocyanate with an isocyanate-reactive component that includes more than 50 equivalent percent of a high molecular weight polyoxyalkylene diol having an unsaturation level no greater than about 0.015 meq/g and up to about 50 equivalent percent of a polytetramethylene ether glycol.

Description

A7 B7 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1288759 V. Technical Description The present invention relates to a block polyurethane/urea which has excellent elasticity, mechanical and thermal properties and relates to Fibers made from such elastomers and methods of making such elastomers and fibers. More particularly, the present invention relates to polyamine urethane/urea and spontane elastic fibers produced from isocyanate-terminated prepolymers by reacting isocyanate The chain is obtained by chain extension, the isocyanate-reactive component comprises polytetramethylene ether glycol (PTMEG) and a low unsaturation, high molecular weight of greater than 50 equivalents/c based on the total isocyanate-reactive component. Polyoxyalkylene glycol. 10 JT-view technology Polyurethane/urea elastomers in the form of fibers and films have found wide application in the textile industry. The term "Sponk," is commonly used to describe these elastomers, which are 15 long chain synthetic polymers composed of at least 85% by weight of block polyurethane. The term "elastic fiber," is also used to describe These polymers (for example in Europe). Spunk is used in many different applications in the textile industry, especially in underwear, bodybuilding, bathrobes and elastic clothing or stockings. The elastic fiber may be provided in the form of a core-spun elastomer yarn which is spun around a filament or staple fiber yarn or as a mixture of short fibers and inelastic 20 fibers, the purpose of which is to improve itself not to be highly elastic. The quality of the fabric worn. In the past, yarns made of natural rubber were the only materials that could be used to provide elasticity to fabrics. Spunk, originally developed in the 1950s, has many advantages over such rubber filaments. The most important of these is its higher -3- degree ^ week with the Chinese state (2ΐ〇χ297¥¥Τ-

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1288759 A7 V. Invention description (2) Modulus. By hanging, for a given denier, Spunk's recovery or retraction force is at least twice that of rubber. This makes it possible to manufacture stretch garments with less elastic fibers and therefore is lighter in weight. Additional advantages over natural rubber include the ability to achieve a finer denier, higher tensile strength and wear resistance, and a higher rebound resilience in the case of 5 reported multiples. In addition, Spunk has improved resistance to many cosmetic oils, solvents (10) such as tankers for dry cleaning, and is also highly resistant to oxidation and ozone. In addition, unlike rubber filaments, the spontane elastic fiber can be easily dyed with certain classes of dyes. 10 Highly stretchable, low modulus fibers are especially desirable. U.S. Patents 4,772,677 and 5,000,899 disclose methods for making such fibers. However, the materials required for the process disclosed in U.S. Patent No. 5, 〇〇〇, 899 make the product fibers economically unattractive. It is known that polyurethane elastomers can be reacted by high molecular weight, substantially linear polyols, polyisocyanates and reactive hydrogen atoms by addition polymerization in a highly polar organic solvent. The manufacture of chain extenders. Polyurethane elastomers obtained from these solvents and the formation of fibers, filaments, yarns and films by reactive spinning are also known. See, for example, U.S. Patent Nos. 3,483,167 and 3,384,623, the disclosure of which are incorporated herein by reference. Spunk made of PTMEG-derived prepolymer and polymer, without the elongation or low hysteresis of natural rubber, is characterized by improved retractive force, higher tensile strength And better resistance to oxidation, old -4-

A7 B7 1288759 V. Description of invention (3) Ability to change. These improved properties have made PTMEG-derived Sponke an industry standard despite the difficulties associated with PTMEG-derived prepolymers and polymers and the high cost of PTMEG itself. For the above reasons, a commercially preferred polymer diol is polytetramethylene 5-ether diol (PTMEG). PTMEG is a solid at room temperature and is capable of producing very high viscosity prepolymers, especially diphenylmethyl diisocyanate ("MDI") prepolymers. However, despite the inherent difficulties in handling PTMEG, the high cost of fibers made with PTMEG and the unsatisfactory hysteresis, PTMEG is producing spunks as no satisfactory alternatives have been found to date. Pillars. A potential alternative to PTMEG, which has been evaluated, is polyoxypropylene glycol ("PPG"), which can in principle be used to make spunk elastic fibers. The manufacture of spunk 15 elastane from prepolymers made from polyol components consisting primarily of PPG is attractive because, from an economic standpoint, the cost of PPG is significantly lower than PTMEG. Further, fibers produced from prepolymers made of PPGs have excellent elongation and retraction or retention. ppGs themselves are easier to handle than PTMEG's because they are low-pour liquids that are not crystalline. In contrast, PTMEGs usually depend on the grade added to it and it is 20 solids. For example, U.S. Patent No. 3,180,854 discloses polyurethane/urea fibers based on prepolymers prepared from polyoxypropylene glycol having a molecular weight of 2 moles. However, the properties of polyoxypropylene-derived spunk elastic fibers are generally inferior to those based on PTMEG. Therefore, polyoxypropylene glycol has not been

1288759 A7 _ B7 V. INSTRUCTIONS (4) Commercially used for Spunk production. See, for example, the Polyurethane HANDBOOK (edited by Gunther Oertel, published by Carl Hanser Verlag, Munichl 985, p. 578), in which polyoxypropylene glycol has hitherto been used only in experimental products. 5 segments of flexible chain because of the poor elasticity of the products produced by them. (p. 578) High molecular weight polyoxypropylene diols produced by conventional methods contain a high percentage of terminal unsaturation or substances containing monofunctional hydroxyl groups. ("monohydric alcohol"). Many people believe that monohydric alcohol acts as a chain terminator, limiting the formation of high molecular weight polymers required during chain extension, thus producing 10 products that are generally of superior quality to PTMEG-derived elastomers. The majority of polyoxyalkylene polyether polyols are polymerized in the presence of a pH-basic catalyst. For example, polyoxypropylene glycol is catalyzed by a base. A difunctional initiator such as the propoxylation of propylene glycol. During base-catalyzed propoxylation, the competitive rearrangement of propylene oxide to allyl alcohol is constantly reversed. The reactor is internally loaded with an unsaturated, monofunctional alkoxylated material. The alkoxylation of the monofunctional material produces an allyl-terminated polyoxypropylene monool. The rearrangement is in the block and BLOCK AND GRAFT POLYMERIZATION, Vol. 2, Ceresa ed., John Wiley & Sons, pages 17-21. 20 Unsaturation According to ASTM D-2849-69 "Testing Polyurethane Foams The measurement was carried out by "Testing Urethane Foam Polyol Raw Materials" and expressed as milliequivalents (meq/g) of unsaturation per gram of polyol. Due to the continuous formation of allyl alcohol, and subsequent propoxylation , -6· This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) ---- 1288759 A7 B7 V. Description of invention (5) The average functionality of this polyol mixture decreases and the molecular weight distribution is broadened. The catalyzed polyoxyalkylene polyol contains a relatively large amount of a lower molecular weight monofunctional substance. In a 4000 Da molecular weight polyoxypropylene glycol, the monofunctional substance content may be between 30 and 40 mole percent. In this In this case, the average functionality of 5 is reduced from nominal or theoretical functionality of 2.0 to about 丨.6 to 1.7. Furthermore, the polyol has two polydispersities due to the presence of a substantial amount of low molecular weight fraction. Mw/Mn. Therefore, lowering the degree of unsaturation in the polyoxypropylene polyol and the accompanying large amount of the monool fraction has been a means of producing an improved polyurethane 10 elastomer. For example, the use of low monofunctional content polyols has been suggested as a means of extracting the molecular weight of two polymers; and increased polymer molecular weight is also believed to be desirable in the production of higher performance polymers. It is not feasible to reduce the degree of unsaturation of the polyoxyalkylene polyol by lowering the catalyst concentration and lowering the reaction temperature, because although a polyol having a low 15 degree of unsaturation can be produced, the reaction rate is too slow, so that propoxyl It takes a few days or even weeks to base. Therefore, efforts have been made to find a catalyst which is capable of producing a polyoxypropylene product in a reasonable period of time and which is not converted into a monofunctional group by an allyl group. Printed by the Ministry of Economic Affairs, the Intellectual Property Bureau, and the Consumer Cooperatives. In the early 1960's, a double metal cyanide 20 catalyst such as hexacyanocobaltate was developed. No. 3,427,256; Although the level of unsaturation is reduced to approximately 0.018 meq/g, the cost of these catalysts in conjunction with the need for lengthy and expensive catalyst removal steps hinders the use of these catalysts to produce polyoxyalkylene paper grades for the Chinese National Standard (CNS). A4 size (210x297 public) 1288759

Industrialization of the polyol process. Other alternatives to basic catalysts, such as oxyhydrin and cesium hydroxide, are disclosed in U.S. Patent 3,393,243. The ruthenium and osmium oxide and ruthenium oxide catalysts (disclosed in U.S. Patent Nos. 5, 187 and 5,114, 619) are capable of achieving certain improvements in the level of 5 unsaturation. However, catalyst costs and toxicity in some cases and the limited improvement in levels attributable to these catalysts hinder their industrialization. Catalysts such as calcium naphthenate and mixtures of calcium naphthenate and tertiary amines have been shown to be useful in the manufacture of unsaturation levels as low as 〇16〇q/g and more generally in the range of 〇·〇2 to 0.04 meq/g. Polyhydric 1 sterol. (See, for example, U.S. Patents 4,282,387, 4,687,851 and 5,010,117, the use of double metal cyanide complex (DMC) catalysts in the 1980s. Improvements in catalytic activity and catalyst removal methods have facilitated the short-term industrial application of DMC-catalyzed polyols with low levels of unsaturation (〇〇15 to I5 0.018 meq/g). However, base catalysis is still the primary method for the production of polyoxypropylene polyols, and pH-testing catalysts are still the catalysts used primarily in commercial polyoxyalkylene polyol production processes. Major developments in DMC catalysts and polyalkoxylation methods have been produced by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumers' Cooperatives. This has enabled the production of ultra-low unsaturation polyoxypropylene polyols on an industrial scale of 20. When catalyzed by these modified DMC catalysts, high molecular weight polyols (having a molecular weight in the range of 4000 Da to _ 〇 Da) typically have an unsaturation level ranging from 〇 〇〇 4 to me 〇〇 7 meq/g. At this level of unsaturation, there is only 2 mole percent or less of monofunctional material. -8- The paper size of these polyols is suitable for the standard of the company (CNS) A4 specification (21G X297 public ® )----- 1288759 A7 B7 V. Invention description (Ο Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Printed GPC analysis shows that they are actually monodisperse and typically have a polydispersity of less than 1.10. Recently, several of these polyols have been commercialized as ACCLAIMTM polyols. U.S. Patent 5,340,902 discloses It is advantageous to have an unsaturation level of less than 0.03 meq/g in the production of gram of elastane fiber, but does not provide any example of producing a spunk elastic fiber using a polyol having an unsaturation level below O OSmeq/g. Patent 5,691,441 discloses that blends of low monohydric alcohol polyols having an unsaturation level below 0.010 meq/g are required to achieve the disclosed invention. U.S. Patent 5,691,441 also teaches "already found that ultra low unsaturation multiples Alcohols are significantly different from both ordinary polyols and low unsaturation polyols. According to this teaching, it can be considered that PTMEG and higher level unsaturation (above 0.010 meq/g) are considered. Spunks made from oxypropylene glycol blends will be significantly inferior to PTMEG and polyoxypropylene glycols based on ultra-low level unsaturation (ie less than 0.010 meq/g). The properties of the fibers of the blend. U.S. Patent 5,691,441 also teaches that polyoxypropylene diols containing ultra-low levels of unsaturation should be used in an amount of from 5 to 50 equivalent percent of the total polyol component. It would be economically advantageous to be able to produce spunk elastic fibers from polyaminophthalate/urea using as much cheaper PPG as possible and as much as less expensive PTMEG. 10 15 Inventors The purpose is to provide a poly-9-meter paper that can be used to produce spun elastic fibers. The scale of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210x297 mm). A7 B7 !288759 V. Inventive Note (8) Amino A An acid ester/urea produced from an isocyanate-terminated prepolymer made with an isocyanate-reactive component, wherein more than 50 equivalent percent of the isocyanate-reactive component is PPG, produced by Spang Acrylic fiber has a make-up with 100% PTMEG A physical property of a Bunker elastic fiber. Another object of the present invention is to provide a process for producing a polyamino acid ester/urea and a spunk elastic fiber produced from such a polyamino phthalate/urea, wherein The superior physical properties of the fibers made with PTMEG are obtained, and the prepolymer viscosity and fiber hysteresis are reduced. 10 A further object of the invention is to provide polyurethanes and ureas and from such polyaminocarboxylic acids The ester/urea-produced spun elastic fibers are based in part on less expensive and easily handled polyoxypropylene diols and have improved properties compared to spunk elastic fibers produced with PTMEG alone. Another object of the present invention is to provide an economically advantageous method of spun elastic fibers and the production of a highly stretchable, low modulus spunk. These and other objects which will be apparent to those skilled in the art from the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, by chain extension of the isocyanate-terminated prepolymer in the presence of a solvent, the isocyanate-terminated prepolymer Producing a polyol component comprising: (1) at least one PTMEG and (2) greater than 50 equivalent percent of at least one of 20 polyoxypropylene diols having a molecular weight greater than about 1500 Da and an unsaturation level Below 0.015 meq/g. Then, the polyaminocarbamic acid g/urea thus obtained is spun into fibers. Detailed Description of Implementation Implementation -10- This paper scale applies to National Standard (CNS) A4 specification (21〇χ297 public)--- 1288759

The present invention relates to polyamine phthalates/ureas suitable for the production of spun elastic fibers, spunk elastic fibers produced from these polyurethanes/ureas, and such polyurethanes/ureas and s The production method of Bunker elastic fiber. The polyurethane/urea of the present invention is produced by chain extension of a isocyanate-blocked prepolymer in the presence of a solvent. Suitable prepolymers are produced by reacting an isocyanate-reactive component generally consisting of a diol with an excess of diisocyanate. The isocyanate-terminated prepolymers typically used to produce such polyurethanes/ureas typically have a lower isocyanate content. An isocyanate content of from about 1 to about 3.75% is preferred. Particularly preferred prepolymers have an isocyanate content of from 1. 5 to 3.5 %, most preferably from 1. 5 to 2.5. The prepolymer is then chain extended in solution. A key feature of the invention is the isocyanate-reactive component used to make the isocyanate-terminated prepolymer. The isocyanate-reactive component, typically a polyol component, comprises: (1) at least 5 eq% to 15 less of a high molecular weight, low unsaturation polyoxypropylene diol and (2) at least one PTMEG 〇 The high molecular weight polyoxypropylene glycol component used in the present invention printed by the Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative must have an unsaturation level of less than or equal to 015.015 meci/g. The isocyanate-reactive component used to produce the guanidinium-terminated prepolymer should comprise up to 2% by weight (based on total isocyanate-reactive components) The high molecular weight, low unsaturation polyoxypropylene diol of weight) is preferably from about 50 to about 90 equivalent percent, more preferably from about 5 Torr to about 75 equivalent percent. The high molecular weight polyoxyalkylene glycol present in the isocyanate-reactive component has an unsaturation level of less than 015.015 meq/g, more preferably less than

1288759

O.Oimeq/g and most preferably less than or equal to me5meq/g are printed by the Intellectual Property Office of the Ministry of Economic Affairs. However, it is also within the scope of the invention to include a small number of high molecular weight polyoxypropylene polyol knives having a high level of (4) high unsaturation. In this case, the actual unsaturation of the high molecular weight polyoxypropylene glycol component is still about 50. 〇15 meq/g or less. • The term “low unsaturation polyoxypropylene glycol” as used herein refers to a total of products produced by propoxylated di-based initiators prepared by the use of propylene oxide in the presence of a catalyst. The degree of unsaturation is less than or equal to 〇.〇15meq/g. The polyoxypropylene diol may comprise an epoxy bromide moiety in a randomly distributed or enemy form. If the epoxy moiety is stored, the block is preferably end-embedded, and when an epoxy-containing portion is present, it is preferably a randomly distributed portion of the epoxy. Typically, the poly15, propyl diol should not contain more than about 3% by weight of epoxide, enamel, preferably no more than 2% and more preferably no more than about 1%. Oxygen f垸 part. The mercaptotriol may also contain higher order dilute oxygen = for example, derived from 2,3_butylene oxide and other higher order alkylene oxide or oxetane. The amount of such higher-order alkylene oxide may be up to 1 - 3 % by weight based on the poly 20 oxypropyl polyol. Preferably, however, the oxypropylene diol is derived substantially from a mixture of propylene oxide or propylene oxide oxirane. All such polyols in which the major portion is a propylene oxide moiety are considered to be polyoxypropylene glycols herein. The high molecular weight, low unsaturation polyoxypropylene-alcohols useful in the practice of the present invention typically have a molecular weight of at least about 1500 Da, preferably at least -12. Specifications (210x297b)

1288759 A7 B7 V. INSTRUCTIONS (U) Approximately 2000 Da and may be up to 20,000 Da or higher. It is especially preferred that the molecular weight is in the range of from about 3000 Da to about 8,000 Da and most preferably is in the range of from about 4000 Da to about 8000 Da. Methods for producing such polyols are known to those skilled in the art. In addition, such polyols are commercially available. Here, "molecular weight" and "equivalent weight" are represented by Da (Dalton), and are number average molecular weight and number average equivalent weight, respectively, unless otherwise stated. For each polyether diol, the number average molecular weight is determined from the hydroxyl value of the polyether diol, which is determined by the imidazole-pyridine catalyst method described in S. L. Wellon et al. Determination of Hydroxyl Content of Polyurethane Polyols and Other Alcohols w , Analytical Chemistry (ANALYTICAL CHEMISTRY), Vol. 52, ΝΟ·8, pp. 137屯1376 (1980) July) 15 Of course, more than one type of high molecular weight polyoxypropylene poly-Ministry of Intellectual Property Intelligence Bureau of Peasant Consumer Cooperatives can be used to print alcohol blends, or in small quantities (ie less than 10%) Weight) Adding a low molecular weight S: diol. In the practice of the present invention, a mixture of polyoxypropylene diols having different levels of unsaturation may also be used. Of course, a level of unsaturation greater than 0.015 meq/g may be used. Alcohol. 20 However, when such blends are used, the high molecular weight component blend should have an average molecular weight of at least 1500 Da and an average level of unsaturation should still be no greater than 0.015 meq/g. Preferably, the preform The material is manufactured from those derived from substantially all difunctional polyols, especially polyoxypropylene glycol. The term "polyoxypropylene-13" applies to the Chinese National Standard (CNS) A4 specification (210x297). PCT) A7 B7 1288759 V. INSTRUCTION DESCRIPTION (12) The base diol "includes a small amount, i.e., up to about 5 weight percent or more of a triol. The polyurethane used to produce the polyurethane of the present invention. Tetramethyl ether glycol (PTMEG) has a molecular weight above 6 〇〇 Da, preferably from about 600 to about 5 6,000 Da, most preferably from about 6 〇〇 to about 3, 〇〇〇 Da. The PTMEG can pass Any known method of manufacture. A suitable method is the polymerization of tetrahydrofuran in the presence of a Lewis acid catalyst. Suitable polymerization catalysts include anhydrous aluminum oxide and boron trifluoride etherate. Such catalysts are well known and many Subjects of Patents and Publications. 10 PTMEG polyols are commercially available from a variety of sources in a variety of molecular weights, for example,

DuPont sells PTMEG polyols under the trademark Terathane®. BASF

Corporation sells PTMEG polyols under the name p〇iyTHF. Penn

Specialty Chemicals ’ Inc. sells this polyol under the trademark POLYMEG®. 15 The isocyanate-reactive component printed for the production of the spun elastic fiber of the present invention for producing the spunk elastic fiber of the present invention is mainly a diol component, which is preferably composed of the following Composition: (1) from about 10 equivalent percent to about 5 equivalent percent of PTMEG and more preferably from about 25 to about 5 equivalent percent of PTMEG; (2) at least 50 equivalent percent of polyoxypropylene glycol component The polyoxypropylene glycol component has an average degree of unsaturation of less than or equal to 0.015 meq/g, more preferably from about 5 to about 9 equivalent percent of such polyoxypropylene glycol, Most preferably from about 5 〇 to about 75 equivalent percent of such polyoxypropylene diol; and optionally (3) a small amount (i.e., up to 1 〇〇/〇) of another polyol or having at least one isocyanate _reaction The sex group's -14- 1288759 B7 V. Description of the invention (13 5 10 15 Ministry of Economic Affairs, Intellectual Property Bureau, Bayer Consumer Cooperative, printed 20 other materials. = Known aliphatic and / or aromatic diisocyanine - Isocyanate S-terminated prepolymer of the present invention Production includes: linear aliphatic isocyanate vinegar, for example: isocyanate, 1,3-propylene diisocyanate, 14_ stilbene diisocyanate hexamethylene diisocyanate, - octylene II Alien; root--2,2,4·trimethylpentane, 3_oxo#pental II|-isocyanate, etc. diisocyanate_2, cyanate S曰, preferably hexane diiso Cyanate gas = such as tetramethyl dimethyl dimethyl sulfonate::; oxyacetate and hydrogenated methylene diphenylidene diisocyanate and aromatic monoisocyanate such as toluene diisocyanate, Eurasian methyl diphenyl stearyl diisocyanate, especially 4,4, methylene = cyanic acid: 4, _MDI) ... xylylene diisocyanide and the like. 4,4'-MDl is especially preferred. The isocyanide-reactive component and the excess amount of the desired diisole acid vinegar are preferably in an inert atmosphere T or under vacuum at a ship elevated temperature, ie between 5 (TC and loot:, more preferably The reaction is carried out between 6 Torr and 9 Torr. The amount of isocyanate excess is selected such that the % NCO group content provided in the prepolymer is between about ι·〇 weight percent and 375 wt%, preferably 1· Between 5 and 3.5 weight percent, most preferably from about 1.5 to about 2.5 Torr, the reaction of the isocyanate with the isocyanate-reactive component can be carried out using any known reaction capable of catalyzing the isocyanate and hydroxylamine groups-15 - The paper scale applies to the Chinese National Standard (CNS) A4 specification (210x297 mm). 5. Catalyst catalysis of invention (14), but the reaction can also be carried out without a catalyst. In the preferred embodiment of the invention In the embodiment, the catalyst used is a metal salt or a soap of 匕C2〇monocarboxylic acid or naphthenic acid. The octanoic acid is especially selected from the group 5. In another preferred embodiment of the invention, it has been found that Pre The polymer-forming reaction is carried out in the presence of at least 5% by weight of dimethylacetamide, preferably at least 10% of dimethylacetamide, without the need for a catalyst, and the prepolymer-forming reaction can be 50 to 6 Torr. (at a temperature of: 10) Typically, the reaction of the isocyanate-reactive component and the isocyanate component proceeds until the isocyanate content becomes constant. ~ Then, the isocyanate is usually sealed. The terminal prepolymer is dissolved in a polar aprotic solvent such as dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc., and then any known chain extender 15 is used. Chain extension is carried out. Aliphatic diamines such as ethylenediamine are one of the most preferred. The term polar aprotic solvent "herein" means having the ability to dissolve the chain extended polyurethane at a desired concentration, while a solvent that is substantially non-reactive with isocyanate groups. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, in one embodiment of the invention, comprising at least one asymmetric aliphatic 20 aliphatic and/or cycloaliphatic diamine and at least One kind The chain extender component of the diamine is used to extend the chain of the isocyanate-terminated prepolymer. The aliphatic and/or cycloaliphatic diamine is present in an amount based on the total amount of the chain extender component. Equivalents, preferably from about 7 to about 25 equivalent percent, more preferably from about 7 to about 20 equivalent percent, and most preferably from about 1 Torr to about 15 equivalents of hundred-16 - the paper scale applies to the Chinese national standard (〇^ ) Α 4 specifications (2i 〇 x 297 mm) """ Ministry of Economic Affairs Intellectual Property Bureau Bayer Consumer Cooperative Printed 1288759 V. Invention Description (15) Fraction P The remainder of the chain extender component is linear Amines Examples of suitable aliphatic and/or cycloaliphatic chain extenders include 1,2-diaminopropanol; isophoronediamine 'methyldiaminecyclohexane; I,3- Diaminocyclohexane; 2-methylpentamethylenediamine (available under the name Dytek A 5 from DuPont); 1,4-diamino-dimethylpyrazine; 1,4-diamino- 2,5-Dimethylpyrene; and methyl double "propylamine. Examples of suitable linear amine extenders include: ethylenediamine; hydrazine; 1,3-propanediamine; and butylenediamine. Ethylenediamine is most preferred. The polyurethane/urea thus produced has both a hard segment and a soft segment. The term "soft segment" and "hard segment" refer to a specific portion of the polymer chain. The soft segment is a polyether base moiety of a block polyurethane/urea derived from PTMEG and polyoxypropylene glycol. The hard segment is the portion of the polyurethane/urea chain derived from the diisocyanate and the chain extender. The term "NCO content" refers to the amount of isocyanate groups of the prepolymer prior to chain extension. 15 A chain terminator is typically included in the reaction mixture to adjust the final molecular weight and intrinsic viscosity of the polyurethane/urea polymer to the desired value. Typically, the chain terminator is a monofunctional compound such as a secondary amine (e.g., diethylamine or dibutylamine). The polyurethane/urea and spunk elastic fibers of the present invention can be produced by any method known to those skilled in the art for producing the Sponbond Polymer 20. Such a method is disclosed in, for example, U.S. Patent Nos. 3,384,623; 3,483,167 and 5,340,902, the disclosure of each of each of each The invention has been described above generally, and the invention may be further understood by reference to the following specific embodiments, which are provided herein only for the

1288759 A7 A7 ____ B7 V. INSTRUCTIONS (16) The purpose of the description is not intended to limit the invention unless otherwise stated. EXAMPLES Measurement Method 5 The properties of the spunk material produced in the examples were determined as follows: (1) Intrinsic viscosity of the elastomer 7? Dilution at a concentration c of 0.5 g/100 ml of dimethyl ethanoamine The solution was measured at 30 ° C, wherein the relative dryness with respect to the pure solvent was determined to be 77 r, and was converted according to the following formula: 10 7) r = tl / t 〇 where: one h is the elution time of the polymer solution (seconds) T〇 is the elution time of pure solvent (seconds) η = (Ln η r) / c 15 (2) Toughness and elongation are determined in accordance with DIN 53 815 (cN / dtex). Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative (3) Permanent deformation or permanent elongation is measured after 5x300% elongation, and the recovery time between the two is 60 seconds. Permanent deformation is a measure of the ability of a fiber to be stretched and then returned to its original length. Any increase in measurement is a permanent deformation rate or permanent elongation, and a low value is desirable. Typical 20 PTMEG-derived Spunk elastic fibers have a % permanent deformation of less than 30%, preferably less than 25°/〇. The materials used in the examples were as follows: Polyol A: propylene oxide-based diol having a number average molecular weight of 2,000 and an unsaturation level of 0.005 meq/g. •18- This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1288759 A7 B7 V. Invention Description (17) Polyol B: Polytetramethylene Ether II The alcohol has a number average molecular weight of 2,000. Polyol C: polyoxypropylene diol having a molecular weight of 4000 Da and an unsaturation level of 0.005 meq/g. Polyol D: polytetramethylene ether glycol having a number average molecular weight of 2,900. 5 Polyol E: a blend of polyoxypropylene diol having a molecular weight of 4000 Da and an unsaturation level of me 30 q 30 meq/g, and a molecular weight of 4000 Da and an unsaturation level of the blend. 0.020 meq/g. MDI: 4,4'-diphenylmethane diisocyanate. ZNO: octanoic acid (8% octanoic acid solution in dimethyl acetamide). 1〇 DMAc ··Dimethylacetamide. EDA: ethylenediamine. IPDA: isophorone diamine. DEA: diethylamine. 15 Example U Comparative) 2400 gm of Polyol A was dehydrated in vacuum at 120 ° C for 1 hour. After cooling to room temperature, 50 ppm of ZNO was mixed into the polyol. 512.7 gm of MDI was added at 62 °C. The reaction mixture was heated at 70 ° C for 45 minutes until the NCO content of the prepolymer was 2.44%. 20 1248 gm of DMAc was added to the prepolymer at 60 ° C, and the mixture was cooled to 25 °C. The mixture of homogenized prepolymer and DMAc had an NCO content of 1.63%. 21.08 gm of EDA, 52.52 gm of DEA and 2317 gm of DMAc were added to a 1700 gm diluted prepolymer under rapid mixing. After mixing for one hour, the resulting solution had a viscosity of 38 Pa.s.

-19-

1288759 Λ7 ___ B7 V. Description of invention (18) Degree. An additional 63.8 gm of the diluted prepolymer was added and then mixed for 3 minutes. At this time, the viscosity of the solution was 56 Pa.s. An additional 38.3 gm of the diluted prepolymer was added and then mixed for 30 minutes. To the viscous polymer solution, 0.3% by weight of magnesium stearate, 5.2% by weight of Cyanox® 1790 antioxidant (available from Cyanamid), and 5% by weight of Tinuvin® 622 stabilizer (available) From ciba_Geigy) and 〇·3°/❶ weight of polyether siloxanes Silwet® L7607 (Union Carbide

The product of Corp. 'USA' (the amount is based on polyurethane solids). The final solution was obtained in this way, and its viscosity, solid content and intrinsic viscosity are listed in Table 1 10. The solution was then dry spun to form 4 denier fibers. The relative amounts of materials used and the properties of the polymer solution and fibers made from the solution are listed in the Table. 15 Examples 2-4 The procedure of Example 1 was repeated using the materials listed in Table 1 in the relative amounts listed in Table 。. The properties of the polymer solution and the fibers made with these solutions are also listed in Table 1. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -20- 1288759 A7 B7 V. Invention Description (19) Table 1 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Example 1* 2 3* 4 Equivalent % Polyol A 100 75 0 60 wt% polyol A 100 68 0 60 equivalent % polyol D 0 25 0 0 wt% polyol D 0 32 0 0 wt% polyol B 0 0 100 40 equivalent % polyol B 0 0 100 40 blend Molecular weight 2000 2194 2000 2000 NCO: OH 1.7 1.7 1.65 1.7 Prepolymer viscosity Pa.s 8 16.9 51 18.1 Prepolymer catalyst 50ppm ZNO 50ppm ZNO No 50ppm ZNO EDA, Molar% 99.0 82.5 95.0 82.5 IPDA, Moer% 0 15 0 15 DEA, Moer% 1.0 2.5 5.0 2.5 Polymer solution % solid 30 30 30 30 Viscosity @50°C Pa.s 54 69 59 89 Intrinsic viscosity, dL/g 1.261 1.267 1.269 1.556 Spinning speed (m/min .) 420 420 420 420 Fiber Performance Toughness (cN/dtex) 0.43 1.15 1.52 1.31 Actual Toughness 1 (cN/dtex) 3.29 8.96 10.79 9.37 -21-

This paper scale applies to China National Standard (CNS) A4 specification (210x297 mm) 1288759

V. Description of the invention (20)

% elongation 400% modulus cN/dtex 5th cycle unloading capacity @150%, cN/dtex permanent deformation %

608 615 0.326 0.216 0.021 0.022 15 21 *Comparative example Actual degree - the degree of erection calculated on the basis of the actual denier of the material. 5 10 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printing 15 As can be seen from the data in Table 1, prepolymer solutions (Examples 2 and 4) produced in accordance with the present invention, and made with individual pTMEG The prepolymer solution (Example 3) has a significantly lower dryness compared to the prepolymer solution. The fibers produced in accordance with the present invention (Examples 2 and 4) have good mechanical properties. This is especially surprising given that these systems contain a low percentage of 1>7]^]£(} (25 and 4 eq equivalent %, respectively). The fibers produced in Example 1 without pTMEG are not acceptable. Toughness and permanent set. Comparing Comparative Example 1 and Example 2, it is particularly surprising that the addition of such a small amount of PTMEG resulted in a significant improvement in fiber properties, although the fibers produced in Examples 2 and 4 were The tenacity values are not as high as the strength values of the fibers made with pTMEG alone (Comparative Example 3), but the fibers have many desirable properties such as higher elongation, lower modulus, and lower permanent Deformation. Higher elongation is especially attractive in yarn covering operations because more weight of spunk can be used to cover more yarn (ie, yield is more south). -22-This paper size applies. China National Standard (CNS) A4 specification (210x297 mm) 1288759

Not only do these benefits, the fibers of the present invention (Examples 2 and 4) have the same fifth cycle 150% unloading or retractive force as fibers produced using a polyol component based on 10% PTMEG. Low modulus is attractive because it means that the fibers are easier to stretch and have less resistance. 5 A combination of low modulus and high unloading or retractive force, the fibers produced in accordance with the present invention are described as having low hysteresis. Examples 5-7 The procedure of Example 10 was repeated using the materials listed in Table 2 in the relative amounts listed in Table 2. The physical properties of the produced fibers were determined and are listed in Table 2. These properties are then compared to the physical properties of commercially available low modulus fibers. 15 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Example 5 6 7* Commodity Fiber 2 Equivalent % Polyol C 65.02 65.02 —- ___ Weight % Polyol C 78.77 78.77 — Equivalent % Polyol E —- --- 65.23 Weight % Polyol E — 78.74 eq% Polyol B 34.98 34.98 34.77 _ _ % by weight Polyol B 21.23 21.23 21.26 Total molecular weight of the blend (Da) 3284 3284 3259 -2 Moderate ruler paper standard standard home country secret 97 2 X ο 1288759 A7 _ B7 Description of invention (22) V. NCO: OH 1.8 1.8 1.8 ——— Prepolymer viscosity Pa.s (50°C) 13.6 13.6 13.2 Prepolymer catalyst 50ppm ZNO 50ppm ZNO 50ppm ZNO — EDA , Moer % 97.5 83 83.5 I·· IPDA, Moer % 0 15 15 — DEA, Moer % 2.5 2 1.5 Spinning speed (m/min.) 500 420 420 — Nominal denier 40 40 40 180 Mould Quantity @100%, (cN/dtex) 0.042 0.041 0.037 0.053 Modulus @200%, (cN/dtex) 0.081 0.085 0.075 0.096 Modulus @300%, (cN/dtex) 0-116 0.127 0.109 0.153 Quantity @400%, (cN/dB) 0.156 0.177 0.149 0.228 Toughness g/denier 0 .95 1.09 0.62 0.88 Actual toughness 1 g/denier 8.34 9.03 5.90 7.00 Elongation at break % 779 727 850 694 Permanent deformation % 16 11 17 11 5th cycle loading capacity @150%, cN/dtex 0.025 0.025 0.022 0.026 5 cycles unloading capacity @150%, (cN/dtex) 0.021 0.022 0.019 0.023 ---__ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing *Comparative Example 1 Actual toughness = actual denier at break Based on the calculated toughness. 2 available from DuPont's Lycra 902C fiber. -24- 1288759 at B7 V. INSTRUCTION DESCRIPTION (23) As can be seen from the data in Table 2, fibers produced in accordance with the present invention have low modulus, low hysteresis, high elongation and high retractive force characteristics. . Comparative Example 7 shows that fibers produced using 5 PPG having an unsaturation level of 0.02 meq/g have low toughness. The present invention has been fully described above, and it will be apparent to those skilled in the art that the invention may be modified and modified without departing from the spirit and scope of the invention. Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives 2 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

96· 2· 16 ....丄疒 u Patent Application No. 92114494' ^ ROC Patent Appln. No. 92114494 Corrected unlined patent application text in the text replacement page - Annex (II) Amended Claims in Chinese - Encl. (II) Ministry of Economic Affairs Intellectual Property Office staff consumption The cooperative printed 12887 for 丄4&lt;IM m (February 1996, 丨t曰 sent) VI. Shenqing patent scope (tmitted on February (t, 2007) 1. A block polyurethane/urea, It is a (1) stoichiometric excess of at least one diisocyanate 5 and (2) isocyanate by a) an isocyanate-terminated prepolymer having a free isocyanate group content of from about 1.0 to about 3.75% in solution. A reactive component comprising: (i) a diol component comprising (a) at least 50 equivalent percent of at least one polyoxypropylene diol having a molecular weight of at least 1500 Da and an average of 10 degrees of unsaturation below Or equal to 0.015 meq/g, and (b) up to 50 equivalent percent of at least one polytetramethylene ether glycol having a molecular weight of at least about 600 Da, and 15 optionally, (ii) one or more other materials, comprising At least one a functional group reactive with an isocyanate group, provided that the total number of equivalent weight % of (1) and (ii) is 100 equivalents, the reaction product, 20 and b) a chain extender selected from at least one asymmetric aliphatic group and / or an alicyclic diamine and a linear diamine, which are produced by reacting in the presence of c) a polar aprotic solvent 25. 2. The polyurethane/urea of claim 1 wherein from about 50 to about 90 equivalent percent of said diol component is polyoxypropylene glycol. 3. Polyurethane/urea according to item 1 of the patent application, -26 This paper scale applies to the Chinese national standard iCNSYA4 (格 (210x297 公蝥) 1288759 Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, Printed. 4. Polyurethane _/urea of Patent Item No. 1, wherein two or two to about 75 equivalent percent of the diol component is polyoxypropylene alcohol. = Polyurethane/urea of claim 1, wherein the monoisodecanoate is diphenylmethane diisocyanate. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; According to F, the polyurethane/urea of the first patent range is used for the manufacture of spunk elastic fibers. 8. A method of making a spun elastic fiber, comprising spinning a polyurethane/urea, the polyurethane/urea being: a) a swim, an isocyanate group content of from about 1 Torr. An isocyanate-terminated prepolymer to about 孓?, which is (1) a stoichiometric excess of diisocyanate, and (2) an isocyanate-reactive component comprising (i) a diol component comprising ( a) at least 50 equivalent percent of at least one polyoxypropylene glycol having a molecular weight in excess of about 1500 Da and an average level of unsaturation below or equal to 0.015 meq/g, and (b) up to about 50 equivalent percent of at least one poly a methylene glycol having a molecular weight of at least 6 ODA; and optionally, (ii) one or more other starting materials comprising at least one functional group reactive with an isocyanate group, 5·10 7· 15 20 25 -27 This paper size applies to the Chinese National Standard (CNS) A4 specification (210x297 mm) on four A8 B8 1288759 VI. Scope of Patent Application The condition is that the total number of equivalent weight % of (1) and (ii) is 1 当量 equivalent percentage, and the reaction product of 5 b) chain extender in c) solvent. 9. According to the method of claim 8, the diisocyanate 10 acid ester is diphenylmethane diisocyanate. The method of claim 8, wherein the chain extender comprises at least one asymmetric aliphatic and/or alicyclic diamine and at least one linear diamine. The method of claim 8, wherein the catalyst is present during the manufacture of the 15 prepolymer. The method according to claim 8, wherein the isocyanate and the isocyanate-reactive component are reacted in the presence of at least 5% by weight of dimethylacetamide. The method according to claim 8, wherein the isocyanate 20 ester and the isocyanate-reactive component are reacted in the presence of at least 1% by weight of dimethylthiamine. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. This paper scale applies the Chinese National Standard (CNS) A4 specification (210x297 mm).